WO2012090783A1 - Verre non alcalin et procédé pour la production de verre non alcalin - Google Patents

Verre non alcalin et procédé pour la production de verre non alcalin Download PDF

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Publication number
WO2012090783A1
WO2012090783A1 PCT/JP2011/079479 JP2011079479W WO2012090783A1 WO 2012090783 A1 WO2012090783 A1 WO 2012090783A1 JP 2011079479 W JP2011079479 W JP 2011079479W WO 2012090783 A1 WO2012090783 A1 WO 2012090783A1
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Prior art keywords
mgo
glass
less
cao
alkali
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PCT/JP2011/079479
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English (en)
Japanese (ja)
Inventor
知之 ▲辻▼村
学 西沢
小池　章夫
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旭硝子株式会社
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Application filed by 旭硝子株式会社 filed Critical 旭硝子株式会社
Priority to CN201180062824.6A priority Critical patent/CN103282319B/zh
Priority to EP11852770.4A priority patent/EP2660213A4/fr
Priority to KR1020137016736A priority patent/KR101751569B1/ko
Priority to JP2012550860A priority patent/JP5817737B2/ja
Publication of WO2012090783A1 publication Critical patent/WO2012090783A1/fr
Priority to US13/928,617 priority patent/US9108879B2/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • C03C3/093—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods

Definitions

  • the present invention relates to a non-alkali glass which is suitable for various display substrate glasses and photomask substrate glasses and which is substantially free of alkali metal oxides and can be float-molded.
  • the following characteristics have been required for various display substrate glasses, particularly those in which a metal or oxide thin film is formed on the surface.
  • alkali metal oxide When an alkali metal oxide is contained, alkali metal ions diffuse into the thin film and deteriorate the film characteristics, so that the alkali metal ions are not substantially contained.
  • the strain point When exposed to a high temperature in the thin film forming process, the strain point is high so that the deformation (thermal shrinkage) associated with glass deformation and glass structural stabilization can be minimized.
  • BHF buffered hydrofluoric acid
  • ITO various acids used for etching metal electrodes
  • ITO various acids used for etching metal electrodes
  • resistant to alkali of resist stripping solution Resistant to alkali of resist stripping solution.
  • a-Si amorphous silicon
  • p-Si polycrystalline silicon
  • a glass having a small average thermal expansion coefficient is required to increase productivity and thermal shock resistance by increasing the temperature raising / lowering rate of the heat treatment for producing a liquid crystal display.
  • Patent Document 1 discloses a glass containing 0 to 5% by weight of B 2 O 3
  • Patent Document 2 discloses a glass containing 0 to 5 mol% of B 2 O 3
  • No. 3 discloses a glass containing 0 to 8 mol% of B 2 O 3 .
  • the glass described in Patent Document 1 has a high devitrification temperature because it contains CaO in an amount of 11 mol% or more, and also contains a large amount of impurity phosphorus in limestone, which is a raw material for CaO. There is a risk of causing a leakage current. Further, since the glass described in Patent Document 2 contains 15 mol% or more of SrO, the average thermal expansion coefficient at 50 to 300 ° C. exceeds 50 ⁇ 10 ⁇ 7 / ° C.
  • the glass described in Patent Document 3 is “glass containing 55 to 67% by weight of SiO 2 and 6 to 14% by weight of Al 2 O 3 ” (group a) and “49 to 50% of SiO 2.
  • an alkali-free glass described in Patent Document 4 has been proposed.
  • the alkali-free glass described in Patent Document 4 has a high strain point, can be molded by a float process, and is suitable for applications such as a display substrate and a photomask substrate.
  • An object of the present invention is to provide an alkali-free glass that solves the above-mentioned drawbacks, has a high strain point, has low viscosity, has low devitrification properties, and is easy to float.
  • the strain point is 735 ° C. or more
  • the average thermal expansion coefficient at 50 to 350 ° C. is 30 ⁇ 10 ⁇ 7 to 40 ⁇ 10 ⁇ 7 / ° C.
  • the glass viscosity is 10 2 dPa ⁇ s. a less temperature T 2 is 1710 ° C. as the temperature T 4 which glass viscosity of 10 4 dPa ⁇ s is not more 1340 ° C. or less, there is the devitrification temperature is 1330 ° C.
  • MgO + CaO + SrO + BaO is 16 to 18.2
  • MgO / (MgO + CaO + SrO + BaO) is 0.35 or more
  • MgO / (MgO + CaO) is 0.40 or more and less than 0.52
  • MgO / (MgO + SrO) is 0.45 or more.
  • the alkali-free glass of the present invention is particularly suitable for display substrates for high strain points, photomask substrates, and the like, and is glass that is easy to float.
  • the composition range of each component will be described. If the SiO 2 content is less than 66% (mol%, the same unless otherwise specified), the strain point is not sufficiently increased, the thermal expansion coefficient is increased, and the density is increased. Preferably it is 67% or more. However, if it exceeds 69%, the solubility decreases and the devitrification temperature increases.
  • Al 2 O 3 suppresses the phase separation of the glass, lowers the thermal expansion coefficient and raises the strain point. However, if it is less than 12%, this effect does not appear, and other components that increase the expansion increase. As a result, thermal expansion increases. Preferably it is 13.5% or more. However, if it exceeds 15%, the solubility of the glass may be deteriorated or the devitrification temperature may be increased. Preferably it is 14.5% or less.
  • B 2 O 3 can be added up to 1.5% in order to improve the melting reactivity of the glass and lower the devitrification temperature. However, if it is too much, the strain point is lowered. Therefore, 1% or less is preferable. In consideration of the environmental load, it is preferable that it is not substantially contained (that is, it is not contained except for impurities that are inevitably mixed as impurities, the same applies hereinafter).
  • MgO has the characteristics that it does not increase expansion in alkaline earths and does not excessively lower the strain point and improves the solubility, but if it is less than 6%, this effect does not appear sufficiently. Preferably it is 7% or more. However, if it exceeds 9.5%, the devitrification temperature may increase. Preferably it is 8.5% or less.
  • CaO has the characteristics that it does not increase the swelling in alkaline earth next to MgO and does not excessively lower the strain point than MgO, and further improves the solubility. It does not appear enough. Preferably it is 7.5% or more. However, if it exceeds 9%, the devitrification temperature may increase, or a large amount of phosphorus, which is an impurity in limestone (CaCO 3 ) as a CaO raw material, may be mixed. Preferably it is 8.5% or less.
  • SrO improves the solubility without increasing the devitrification temperature of the glass, but if less than 0.5%, this effect does not appear sufficiently. Preferably it is 1% or more. However, compared to MgO and CaO, the expansion coefficient tends to increase, and if it exceeds 3%, the expansion coefficient may increase.
  • BaO is not essential, but can be contained to improve solubility. However, compared with MgO and CaO, there is a tendency to increase the expansion coefficient. If it is too much, the expansion and density of the glass are excessively increased, so the content is made 1% or less. It is preferable not to contain substantially.
  • ZrO 2 may be contained up to 2% in order to lower the glass melting temperature or to promote crystal precipitation during firing. If it exceeds 2%, the glass becomes unstable or the relative dielectric constant ⁇ of the glass increases. Preferably it is 1.5% or less, and it is more preferable not to contain substantially.
  • MgO, CaO, SrO, and BaO are less than 16% in total, solubility is poor. Preferably it is 17% or more. However, if it is more than 18.2%, there is a risk that the thermal expansion coefficient cannot be reduced. Preferably it is 18% or less.
  • MgO / (MgO + CaO + SrO + BaO) is 0.35 or more, preferably 0.37 or more.
  • MgO / (MgO + CaO) is 0.40 or more and less than 0.52, preferably 0.45 or more and less than 0.52.
  • MgO / (MgO + SrO) is 0.45 or more, preferably 0.5 or more.
  • the alkali-free glass of the present invention does not contain an alkali metal oxide exceeding the impurity level (ie, substantially) in order not to cause deterioration of the characteristics of the metal or oxide thin film provided on the glass surface during panel manufacture. For the same reason, it is preferred not to contain P 2 O 5 substantially. Furthermore, in order to facilitate recycling of the glass, it is preferable that PbO, As 2 O 3 , and Sb 2 O 3 are not substantially contained.
  • the alkali-free glass of the present invention contains ZnO, Fe 2 O 3 , SO 3 , F, Cl, SnO 2 in a total amount of 5% or less in order to improve the solubility, clarity, and float moldability of the glass. it can.
  • the alkali-free glass of the present invention has a strain point of 735 ° C. or higher, preferably 737 ° C. or higher, more preferably 740 ° C. or higher, and can suppress thermal shrinkage during panel manufacture. Further, a solid phase crystallization method can be applied as a method for manufacturing a p-Si TFT. Since the alkali-free glass of the present invention has a strain point of 735 ° C. or higher, it is used for a high strain point (for example, a display substrate for organic EL or a substrate for illumination, or a thin plate having a thickness of 100 ⁇ m or less). Substrate or lighting substrate).
  • the drawing speed at the time of forming tends to increase, so that the fictive temperature of the glass rises and the glass compaction tends to increase. In this case, compaction can be suppressed when the glass is a high strain point glass.
  • the alkali-free glass of the present invention preferably has a glass transition point of 760 ° C. or higher, more preferably 770 ° C. or higher, and further preferably 780 ° C. or higher.
  • the alkali-free glass of the present invention has an average coefficient of thermal expansion at 50 to 350 ° C. of 30 ⁇ 10 ⁇ 7 to 40 ⁇ 10 ⁇ 7 / ° C., has high thermal shock resistance, and has high productivity during panel production. it can.
  • the average thermal expansion coefficient at 50 to 350 ° C. is preferably 35 ⁇ 10 ⁇ 7 to 40 ⁇ 10 ⁇ 7 / ° C.
  • the alkali-free glass of the present invention has a specific gravity of preferably 2.65 or less, more preferably 2.64 or less, and further preferably 2.62 or less.
  • the temperature T 2 at which the viscosity ⁇ becomes 10 2 poise is 1710 ° C. or less, preferably 1700 ° C. or less, more preferably 1690 ° C. or less. It is relatively easy to dissolve.
  • the alkali-free glass of the present invention has a temperature T 4 at which the viscosity ⁇ becomes 10 4 poise is 1340 ° C. or less, preferably 1335 ° C. or less, more preferably 1330 ° C. or less, and is suitable for float molding. Further, the alkali-free glass of the present invention has a devitrification temperature of 1330 ° C. or less, preferably less than 1300 ° C., more preferably 1290 ° C. or less, and can be easily molded by a float process.
  • the devitrification temperature is determined by putting crushed glass particles in a platinum dish, performing heat treatment for 17 hours in an electric furnace controlled at a constant temperature, and observing the surface of the glass and the surface of the glass by observation with an optical microscope. It is an average value of the maximum temperature at which crystals are deposited inside and the minimum temperature at which crystals are not deposited.
  • the alkali-free glass of the present invention preferably has a Young's modulus of 84 GPa or more, more preferably 86 GPa or more, further 88 GPa or more, and further 90 GPa or more.
  • the alkali-free glass of the present invention preferably has a photoelastic constant of 31 nm / MPa / cm or less. Due to the birefringence of the glass substrate due to stress generated during the manufacturing process of the liquid crystal display panel and the liquid crystal display device, a phenomenon in which the black display becomes gray and the contrast of the liquid crystal display decreases may be observed. By setting the photoelastic constant to 31 nm / MPa / cm or less, this phenomenon can be suppressed small.
  • the alkali-free glass of the present invention preferably has a photoelastic constant of 25 nm / MPa / cm or less, considering the ease of securing other physical properties.
  • the photoelastic constant can be measured by a disk compression method.
  • the alkali-free glass of the present invention preferably has a relative dielectric constant of 5.6 or more.
  • the sensing sensitivity of the touch sensor is improved, the driving voltage is reduced, and the power is saved.
  • the glass substrate should have a higher relative dielectric constant.
  • the relative dielectric constant can be measured by the method described in JIS C-2141 (1992).
  • the alkali-free glass of the present invention can be produced, for example, by the following method.
  • the raw materials for each component that are normally used are blended so as to become target components, which are continuously charged into a melting furnace and heated to 1500 to 1800 ° C. for melting.
  • the molten glass is formed into a predetermined plate thickness by the float method, and the plate glass can be obtained by slow cooling and cutting. Since the alkali-free glass of the present invention has relatively low solubility, it is preferable to use the following as a raw material for each component.
  • Silica sand can be used as the silicon source of SiO 2 , but the proportion of particles having a median particle size D 50 of 20 ⁇ m to 27 ⁇ m, a particle size of 2 ⁇ m or less is 0.3% by volume or less, and the particle size is 100 ⁇ m or more.
  • silica sand with a volume of 2.5 vol% or less can suppress the agglomeration of the silica sand and melt the silica sand, facilitating the melting of the silica sand, reducing the number of bubbles, and making the alkali-free glass with high homogeneity and flatness. Since it is obtained, it is preferable.
  • particle size in this specification is the equivalent sphere diameter of silica sand (meaning the primary particle size in the present invention), and specifically, in the particle size distribution of the powder measured by the laser diffraction / scattering method.
  • particle size refers to particle size.
  • “median particle diameter D 50 ” means that the volume frequency of particles larger than a certain particle diameter is 50% of that of the whole powder in the particle size distribution of the powder measured by the laser diffraction method.
  • the particle diameter occupied In other words, it refers to the particle diameter when the cumulative frequency is 50% in the particle size distribution of the powder measured by the laser diffraction method.
  • ratio of particles having a particle diameter of 2 ⁇ m or less and “ratio of particles having a particle diameter of 100 ⁇ m or more” in this specification are measured by measuring the particle size distribution by a laser diffraction / scattering method, for example.
  • the median particle size D 50 of silica sand is 25 ⁇ m or less, it is more preferable because the silica sand can be melted more easily. Further, the ratio of particles having a particle diameter of 100 ⁇ m or more in the silica sand is particularly preferably 0% because the silica sand can be easily melted.
  • Alkaline earth metal source An alkaline earth metal compound can be used as the alkaline earth metal source.
  • Specific examples of the alkaline earth metal compound include carbonates such as MgCO 3 , CaCO 3 , BaCO 3 , SrCO 3 , (Mg, Ca) CO 3 (dolomite), MgO, CaO, BaO, SrO and the like.
  • Oxides and hydroxides such as Mg (OH) 2 , Ca (OH) 2 , Ba (OH) 2 , Sr (OH) 2 can be exemplified, but some or all of the alkaline earth metal source is alkaline earth.
  • the unmelted amount of the SiO 2 component contained in the silica sand is increased, the unmelted SiO 2 is taken into the bubbles when the bubbles are generated in the glass melt and gathers near the surface of the glass melt.
  • a difference in the composition ratio of SiO 2 occurs between the surface layer of the glass melt and a portion other than the surface layer, so that the homogeneity of the glass decreases and the flatness also decreases.
  • the alkaline earth metal hydroxide content is preferably 15 to 100 mol% (MO conversion) out of 100 mol% of alkaline earth metal source (MO conversion, where M is an alkaline earth metal element). ), More preferably 30 to 100 mol% (in terms of MO), and even more preferably 60 to 100 mol% (in terms of MO), the unmelted amount of the SiO 2 component at the time of melting the glass raw material decreases. It is more preferable. As the molar ratio of the hydroxide in the alkaline earth metal source increases, the unmelted amount of the SiO 2 component at the time of melting the glass raw material decreases. Therefore, the higher the molar ratio of the hydroxide, the better.
  • the alkaline earth metal source a mixture of an alkaline earth metal hydroxide and a carbonate, an alkaline earth metal hydroxide alone, or the like can be used.
  • the carbonate it is preferable to use at least one of MgCO 3 , CaCO 3 and (Mg, Ca) (CO 3 ) 2 (dolomite).
  • the alkaline earth metal hydroxide it is preferable to use at least one of Mg (OH) 2 and Ca (OH) 2 , and it is particularly preferable to use Mg (OH) 2 .
  • the alkali-free glass contains B 2 O 3, as the boron source B 2 O 3, can be used boron compound.
  • specific examples of the boron compound include orthoboric acid (H 3 BO 3 ), metaboric acid (HBO 2 ), tetraboric acid (H 2 B 4 O 7 ), and anhydrous boric acid (B 2 O 3 ). It is done. In the production of ordinary alkali-free glass, orthoboric acid is used because it is inexpensive and easily available.
  • a boron source containing boric anhydride in an amount of 10 to 100% by mass (in terms of B 2 O 3 ) out of 100% by mass of boron source (in terms of B 2 O 3 ).
  • the boric anhydride is more preferably 20 to 100% by mass, and further preferably 40 to 100% by mass.
  • orthoboric acid is preferable because it is inexpensive and easily available.
  • the raw materials of each component were prepared so as to have a target composition, and were melted at a temperature of 1500 to 1600 ° C. using a platinum crucible. In melting, the glass was homogenized by stirring with a platinum stirrer. Next, the molten glass was poured out, formed into a plate shape, and then slowly cooled.
  • Table 1 shows the glass composition (unit: mol%), ⁇ OH value of glass (measured by the following procedure as an index of water content in glass, unit: mm ⁇ 1 ), thermal expansion coefficient at 50 to 350 ° C. ( Unit: ⁇ 10 -7 / ° C), strain point (unit: ° C), glass transition point (unit: ° C), specific gravity, Young's modulus (GPa) (measured by ultrasonic method), high temperature viscosity value, Standard temperature T 2 (temperature at which glass viscosity ⁇ becomes 10 2 poise, unit: ° C.) and temperature T 4 that becomes standard for float moldability (temperature at which glass viscosity ⁇ becomes 10 4 poise, unit: ° C.) , Devitrification temperature (unit: ° C.), photoelastic constant (unit: nm / MPa / cm) (measured by the disk compression method), and relative dielectric constant (measured by the method described in JIS C-2141).
  • all the glasses of the examples have a low coefficient of thermal expansion of 30 ⁇ 10 ⁇ 7 to 40 ⁇ 10 ⁇ 7 / ° C., a high strain point of 735 ° C. or higher, and are sufficiently resistant to heat treatment at high temperatures. I can understand.
  • the strain point is 735 ° C. or higher, it is suitable for high strain point applications (for example, a display substrate or lighting substrate for organic EL, or a thin display substrate or lighting substrate having a thickness of 100 ⁇ m or less). ing.
  • the temperature T 2 that is a measure of solubility is relatively low at 1710 ° C. or less and is easy to dissolve
  • the temperature T 4 that is a measure of moldability is 1340 ° C. or less
  • the devitrification temperature is 1330 ° C. or less, preferably Is less than 1330 ° C., and it is considered that there is no trouble such as devitrification during float forming.
  • a photoelastic constant is 31 nm / MPa / cm or less, and when used as a glass substrate of a liquid crystal display, a decrease in contrast can be suppressed. Further, the relative dielectric constant is 5.6 or more, and the sensing sensitivity of the touch sensor is improved when used as a glass substrate of an in-cell type touch panel.
  • the alkali-free glass of the present invention has a high strain point and can be formed by a float process, and is suitable for uses such as a display substrate and a photomask substrate. Moreover, it is suitable also for uses, such as a board

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Abstract

La présente invention porte sur un verre non alcalin qui a une température inférieure de recuit supérieure ou égale à 735 °C, un coefficient de dilatation thermique moyen de 30×10-7 à 40×10-7 /°C à une température de 50 à 350 °C, une température (T2) à laquelle la viscosité du verre devient de 102 dPa•s inférieure ou égale à 1 710 °C, une température (T4) à laquelle la viscosité du verre devient de 104 dPa•s inférieure ou égale à 1 340 °C et une température de dévitrification inférieure ou égale à 1 330 °C et qui comprend, en % en mole en termes de teneurs des oxydes, 66 à 69 % de SiO2, 12 à 15 % d'Al2O3, 0 à 1,5 % de B2O3, 6 à 9,5 % de MgO, 7 à 9 % de CaO, 0,5 à 3 % de SrO, 0 à 1 % de BaO et 0 à 2 % de ZrO2, la somme MgO + CaO + SrO + BaO étant égale à 16 à 18,2, le rapport MgO/(MgO + CaO + SrO + BaO) étant supérieur ou égal à 0,35, le rapport MgO/(MgO + CaO) étant supérieur ou égal à 0,40 et inférieur à 0,52 et le rapport MgO/(MgO + SrO) étant supérieur ou égal à 0,45.
PCT/JP2011/079479 2010-12-27 2011-12-20 Verre non alcalin et procédé pour la production de verre non alcalin WO2012090783A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
CN201180062824.6A CN103282319B (zh) 2010-12-27 2011-12-20 无碱玻璃和无碱玻璃的制造方法
EP11852770.4A EP2660213A4 (fr) 2010-12-27 2011-12-20 Verre non alcalin et procédé pour la production de verre non alcalin
KR1020137016736A KR101751569B1 (ko) 2010-12-27 2011-12-20 무알칼리 유리 및 무알칼리 유리의 제조 방법
JP2012550860A JP5817737B2 (ja) 2010-12-27 2011-12-20 無アルカリガラスおよび無アルカリガラスの製造方法
US13/928,617 US9108879B2 (en) 2010-12-27 2013-06-27 Non-alkali glass, and process for production of non-alkali glass

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JP2010-289425 2010-12-27
JP2010289425 2010-12-27

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US13/928,617 Continuation US9108879B2 (en) 2010-12-27 2013-06-27 Non-alkali glass, and process for production of non-alkali glass

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EP (1) EP2660213A4 (fr)
JP (1) JP5817737B2 (fr)
KR (1) KR101751569B1 (fr)
TW (1) TWI480253B (fr)
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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013161903A1 (fr) * 2012-04-27 2013-10-31 旭硝子株式会社 Verre non alcalin et son procédé de fabrication
WO2014129424A1 (fr) * 2013-02-19 2014-08-28 旭硝子株式会社 Verre exempt d'alcali et son procédé de production
EP2821375A4 (fr) * 2012-02-27 2015-10-28 Asahi Glass Co Ltd Procédé de production de verre non alcalin
WO2015166890A1 (fr) * 2014-04-28 2015-11-05 旭硝子株式会社 Verre non alcalin
JPWO2014087971A1 (ja) * 2012-12-05 2017-01-05 旭硝子株式会社 無アルカリガラス基板
CN113412243A (zh) * 2019-02-07 2021-09-17 Ａｇｃ株式会社 无碱玻璃
WO2021261445A1 (fr) * 2020-06-23 2021-12-30 日本電気硝子株式会社 Panneau de verre non alcalin
JP7060915B2 (ja) 2014-12-12 2022-04-27 日本電気硝子株式会社 無アルカリガラス
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WO2013161903A1 (fr) * 2012-04-27 2013-10-31 旭硝子株式会社 Verre non alcalin et son procédé de fabrication
CN104254500A (zh) * 2012-04-27 2014-12-31 旭硝子株式会社 无碱玻璃及其制造方法
JPWO2014087971A1 (ja) * 2012-12-05 2017-01-05 旭硝子株式会社 無アルカリガラス基板
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CN105073670A (zh) * 2013-02-19 2015-11-18 旭硝子株式会社 无碱玻璃及其制造方法
WO2015166890A1 (fr) * 2014-04-28 2015-11-05 旭硝子株式会社 Verre non alcalin
JP7060915B2 (ja) 2014-12-12 2022-04-27 日本電気硝子株式会社 無アルカリガラス
CN113412243A (zh) * 2019-02-07 2021-09-17 Ａｇｃ株式会社 无碱玻璃
WO2021261445A1 (fr) * 2020-06-23 2021-12-30 日本電気硝子株式会社 Panneau de verre non alcalin
WO2022239742A1 (fr) * 2021-05-10 2022-11-17 日本電気硝子株式会社 Panneau de verre sans alcali

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KR101751569B1 (ko) 2017-06-27
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TW201226353A (en) 2012-07-01
US20130288877A1 (en) 2013-10-31
TWI480253B (zh) 2015-04-11
JP5817737B2 (ja) 2015-11-18
CN103282319A (zh) 2013-09-04
EP2660213A4 (fr) 2014-07-23
KR20130143620A (ko) 2013-12-31

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